Oxyalkylated polymerization products of certain resins containing both hydroxyl and allyl radicals, and method of making same



Patented Nov. 13, 19 51 2,574,547 OXYALKYLATED POLYMERIZATION PROD- UCTS OF CERTAIN RESINS CONTAINING BOTH HYDROXYL AND ALLYL RADICALS AND METHOD OF MAKING SAME Melvin De Groote, University City, Mo., assignor to Petroiite Corporation, Ltd., Wilmington, Del a corporation of Delaware No Drawing. Application August 3, 1950, Serial No. 177,553

22 Claims.

The present invention is concerned with products derived by the oxyalkylation of certain polymerization products, which, in turn, are derived from resins containing both allyl radicals and hydroxyl radicals. Polymerization is the result of conventional polymerization reactions involving the allyl radicals. Oxyalkylation is conducted in a conventional manner with alphabeta alkylene oxide, such as ethylene oxide, propylene oxide, etc. The products so obtained have peculiar properties, and, among other things, are surface-active agents.

Another aspect of the invention is concerned with the method of manufacturing the herein described oxyalkylation products. Such oxyalkylated products having terminal hydroxyl radicals may be used as intermediates for further reaction, such as esterification with higher Iatty acids, with polycarboxy acids, with ethyleneimine, with epichlorohydrin, etc. The ultimate products so obtained have value for various industrial purposes, and again in many instances, represent valuable surface-active agents. Hydroxyl radicals and the manufacture of resins containing both allyl radicals, are described in my co-pending application Serial No. 177,551, filed August 3, 1950.

The polymerization of such resins, as, for example, by drastic oxidation, is described in my co-pending application, Serial No. 177,552, filed August 3, 1950.

Over and above this, such oxyalkylated derivatives are suitable for breaking oil field emulsions or other emulsions of the water-in-oil type, as described in my co-pending application Serial No. 177,554, filed August 3, 1950.

The oxyalkylated polymerized allyl radicalcontaining hydroxylated resins herein described are prepared especially by a six-step procedure:

1) The preparation of phenol-aldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualification: Said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose, the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, as sold by the Oronite Chemical Company, San Francisco,

California. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

(2) The second step involves treating the phenol-aldehyde resin so obtained with an alkylene oxide selected from the class of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide in the radio of at least one and less than two moles oi alkylene oxide per phenolic hydroxyl. The preparation of such derivatives is described in De Groote and wirtel co-pending application Serial No. 99,361., flied June 15, 1949. Said co-pending application illustrates the use of resins in which the hydrocarbon substituent in the rings may have as many as 18 carbon atoms, as previously referred to.

(3) The third step involves the hydrogenation of such oxyalkylated resins, i. e., the conversion 01' the aromatic compounds into the alicyclic analogues. The procedure employed is described in detail in co-pending application of De Groote and Keiser, Serial No. 64,443, filed December 8, 1948. In said last mentioned co-pending application the phenols employed are selected from the same class referred to in U. 8. Patent No. 2,499,370, but needless to say, the process is equally applicable in the class of phenols having as many as 18 carbon atoms in the substituent group, as previously described.

(4) The fourth step involves the treatment of the compounds in the presence of an alkaline catalyst, with allyl glycidyl ether.

(5) The fifth step involves polymerization by means oi a suitable reactant, such as an organic peroxide, or by oxidation of a gaseous oxygencontaining medium, such as aid, or a combination of such procedures, or any other conventional procedure employed for producing polymers from conventional allyl radical-containing materials.

(6) The sixth and final step involves oxyalkylation by means 01' an alpha-beta alkylene oxide selected from the class of ethylene oxide, propylene oxide, butylene oxide, glycide and methyl glycide.

Briefly stated, the present process is concerned with the process and the products obtained by the following procedure, to wit, the process of (a) Reacting a phenol with an aldehyde so as to yield (b) An oxyalkylation-susceptible. fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive towards said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being 01' the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; subjecting said aforementioned resin to oxyalkylation with (0) An alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the aurauev class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycice; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula B10, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals; with the proviso that from about one-half to less than 2 moles of alkylene oxide be introduced for each phenolic nucleus;

(11) Converting said oxyalkylatcd resin into the corresponding alicyclic compound by hydrogenation in presence of a hydrogenating catalyst;

(e) Reacting said hydroaromatic compound with allyl glycidyl ether, with the proviso that at least 2 moles of allyl glycidyl ether be reacted for each alicyclic molecule and not in excess of three times the number of hydroxyl radicals present in said molecule:

(1) Polymerizing said allyl radical-containing hydroaromatic compounds; and

(g) subjecting said polymers to oxyalkylation in the manner hereinafter described.

For purpose of convenience and also for ease of comparison with the aforementioned patent, or aforementioned co-pending ap lications, what is said hereinafter will be divided into six parts:

Part 1 will be concerned with the preparation of the resins;

Part 2 will be concerned with the oxyalkylation of the re ins;

Part 3 will be concerned with the hydrogenation of the resins;

Part 4 will be concerned with the reaction of the alicvclic products with allyl glycldvl ether;

Part 5 will be concerned with the polymerization of the allvl radical-containing alicyclic compounds or products described in Part 4, immediatelv receding; and

Part 6 will be concerned with the oxyalkylation of the organic solvent-soluble polymers described in Part 5, preceding.

PART 1 Reference is made to the following U. S. patents: Nos. 2.499.365; 2,499.366: 2,499.36'7;

2,499,368, and 2,499,370, all dated March '7, 1950, to De Groote and Keiser. scribe phenolic resins of the kind herein employed as initial materials, For practical purposes, the re ins having 4 to 12 carbon atoms are most satisfactory, with the additional C14 carbon atom also being very satisfactory. The increased cost of the C16 and Cm carbon atom phenol renders the e raw materials of less importance at least, at the present time.

For specific descri tion of such resins. reference is made particularly to Patent 2.499.370 and to Examples 1a through 103a of that patent for specific examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol, or a mixture of the same. Such resins are described also in issued patents. for instance, U. S. Patent No. 2.499.365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

PART 2 As has been pointed out previously, suitable resins can be made following the procedures pre- These. patents deviousl described, or, for that matter, can be purch sed in the open market. The second step in the overall process involves the use of an alkylene pxide, such as ethylene oxide, propylene oxide and glycide, or methylglycide. The most suitable oxides, from an economical standpoint, are ethylene oxide'or propylene oxide. Obviously, the apparatus suitable for oxyethylatiovi is also suitable for oxypropylation and will serve, if desired, for use with glycide.

I have prepared a large number of resins oi the kind described in Part 1, preceding, on a laboratory scale varying from a few hundred grams or less to somewhat larger amounts. Needless to say, they are also prepared regularly on an industrial scale. This same statement applies to the preparation of the oxyalkylated products with which this second part is concerned.

For a number of well known reasons, equipment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scale size, is not, as a rule, designed for a particular alkylene oxide. Invariably and inevitably, however, and particularly in the case of laboratory equipment, the design is such as to use any of the customarily available alkylene oxides, i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc.

Oxyethylations and oxypropylations are conducted under a wide variety of conditions. not only in regard to presence or absence of catalyst, kind of catalyst previously described, but also in regard to the time of reaction, temperature of reaction, speed of reaction, pressure during reaction, etc. Oxyalkylations can be conducted at temperatures approximating the boiling point of water or slightly above, as, for example, 115 to 120 C.

Likewise, resins can be oxyalkylated, particularly with ethylene oxide or propylene oxide, using temperatures and pressures which are comparatively high, for instance, temperatures in the neighborhood of 200 0., or in excess thereof, and pressures in the neighborhood of 200 pounds per square inch, or in excess thereof. Such oxyalkylations have been described in aforementioned U. S. Patent No. 2,499,370. Generally speaking, such procedure is employed under conditions where there are more than three points of reaction per molecule, and where the amount of oxide added is comparatively high in ratio to the initial reactant. Such procedure is entirely satisfactory in particular oxyalkylation step described in the instant part, i. e., Part 2.

However, since the amount of oxide is comparatively small, less than two moles per phenolic hydroxyl present in the resin unit, it is apparent that time is not a factor. In other words, it is just as satisfactory to employ a comparatively low temperature and low temperature and low pressure, rather than conditions of oxyalkylation previously mentioned, which result in a rapid reaction rate. For this reason, I have employed conditions of the kind involv ing temperatures of about to 0., and pressures of 30 to 40 pounds, or'less. If an atmosphere of inert gas, such as nitrogen, is present during a reaction, needless to say, the pressures may be somewhat higher.

Such low temperature, low reaction rate oxyalkylations have been described very completely in U. S. Patent No. 2,448,664 to Fife et al., dated September '7, 1948.

As previously indicated, low pressure, low temperature reaction rates may require considerable time, as, for instance, in some of the subsequent examples in the neighborhood of one to two hours. Actually, at 180 to 200 0., such reaction might be conducted in ten minutes or less. In large scale, low temperature operations, the time might be somewhat longer, for instance, 5 to 8 hours. In any event, the reaction is so comparatively short that it is of no marked significance, but it is more'convenient to use these lower temperatures on a laboratory or semi-pilot plant scale.

I have used conventional equipment with two added automatic features:

(a) A solenoid-controlled valve which shuts off the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 110 to 120 C., and

(b) Another solenoid valve which shuts off the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose, where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much. shorter. For reasons which are obvious in light of what has been said previously, I have not found it necessary to use such automatic controls under the conditions of oxyethylation employed in introducing such small portion of alkylene oxide. Controls could be used, if desired, and certainly would be used in high temperature oxyalkylation.

Thus, in preparing the various examples, I have found it particularly advantageous to use laboratory equipment which is designed to permit continuous oxyalkylation, whether it be oxypropylation or oxyethylation. With certain changes, as will be pointed out hereinafter, the equipment can be used also to permit oxyalkylation involving the use of glycide, where no pressure is involved, except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out, the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

The oxyethylation or oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that either a continuous. automatically-controlled procedure was employed, or else a short non-automatic method is used. Indeed, in this instance, the latter is preferred. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately one gallon and a working pressure of 1,000 pounds gauge pressure. This pressure obviously is far beyond any requirement, as far as ethylene or propylene oxide goes, unless there is a reaction of explosive violence involved, due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M.; thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge; manual vent line; charge hole for initial reactants; at leastfone connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cool,-

ing and heating the autoclave, such as a cooling jacket, and preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water, and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclave used in oxyalkylation procedures. In some instances, a larger autoclave was used, 1. e., one having a capacity ranging in the neighborhood of 1% gallons.-

Continuous operation, or substantially continuous operation, was achieved by the use of a separate container to hold the alkylene oxide being employed, particularly ethylene oxide or propylene oxide. The container consists essentia ly of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. In some instances, a larger bomb was used, to wit, one having a capacity of about one gallon. This bomb was equipped, also, with an inlet for charging and an eductor tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists, of course, of therupture disc, pressure gauge, sight feed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

In using the small amounts of oxide involved in ratio to initial reactant, i. e., the phenol-aldehyde resin, one need not employ the automatic devices unless desired. Autoclaves of the kind described are equipped with automatic controls which would shut off the ethylene oxide or propylene oxide in event temperature of reaction passes out of the predetermined range, or pressure in the autoclave passes out of the predetermined range. However, in procedure of the kind herein reported, I have done nothing further than to set the inlet open so the oxide was added in approximately two hours and then proceed to let the autoclave run for a total of three hours to insure completeness of reaction. Pressures in no instance registered more than 30 to 40 pounds and the temperatures varied from to C.

One thing must be borne in mind when operating at these comparatively low temperatures of 'oxyalkylation. When operating at a comparatively high temperature, for instance, between 150 to 200 C., an unreacted alkylene oxide, such as ethylene or propylene oxide, makes its presence felt in the increase in pressure or the consistency of a high pressure. However, at a low enough temperature it may happen that the oxide, such as propylene oxide, goes in as a liquid. If so, and if it remains unreacted, there is, of course, an inherent danger and appropriate steps must be taken to safeguard against this possibility; if need be, a sample must be withdrawn and examined for unreacted propylene oxide, or ethylene oxide. One obvious procedure, of course, is to oxypropylate or oxyethylate at a modestly higher temperature, for instance,

75 to C. Obviously, similar precautions are necessary in the case of ethylene oxide, although it is more reactive than propylene oxide.

I have found it comparatively simple to manually control the temperature of reaction by use of cooling water, steam, or electrical heat to raise or lower the temperature. It will be noted the entire procedure herein involved is much simpler than where low-pressure, low-temperature, lowspeed reactants are employed in an eiiort to bring out the introduction of a comparatively large amount of alkylene oxide. Such procedure is sometimes used, for example, in treating diols or triols with ten to twenty or even thirty times their weight of alkylene oxide.

A word can be included in regard to the use of glycide. This is particularly pertinent, because Part 4 is concerned with a reaction involving allyl glycidyl ether, which reaction is also an oxyalkylation, broadly speaking, and involves a reactant which is comparable to glycide. This is obvious, since glycide is 1hydroxy-2,3-epoxypropane, and allyl glycidyl ether is l-allyloxy-2,3-exoxypropane. As previously pointed out, glycide is an alkylene oxide suitable for use in reaction with phenol-aldehyde resins. If either glycide or methylglycide is employed, no appreciable pressure is involved and no effort need be made to use equipment with automatic controls.

Indeed, in the use of a number of initial reactants with glycide, the entire equipment was used almost as if it were an ordinary piece of nonpressure laboratory equipment, since such reactions can be so conducted. Due to the high boiling point of glycide, one can readily employ a separable glass resin pot, as described in U. S. Patent No. 2,499,365, dated March '7, 1950, to De Groote et al., and offered for sale by numerous laboratory supply houses. Equipment of this kind has been advertised extensively in current chemical journals.

If such arrangement is used to prepare laboratory-scale duplications, then care should be taken that the heating mantle can be removed rapidly, so as to allow for cooling; or better still, through an added opening at the top of the glass resin pot or comparable vessel should be passed a stainless steel cooling coil so that the pot can be cooled more rapidly than by mere removal of mantle. If a stainless steel coil is introduced,

it means that the conventional stirrer of the paddle type is changed to one of the centrifugal type, which causes the fluid or reactants to mix, clue to swirling action in the center of the pot. Still better is the use of a metal laboratory autoclave of the kind previously described above, but

in any event, when the initial amount of glycide is added to a resin, for example, in order to convert it into an oxyalkylated derivative, speed of reaction should be controlled by the usual factors such as (a) the addition of glycide; (b) the elimination of external heat; and (c) the use of cooling so there is no undue rise in temperature. All the foregoing is merely conventional, but is included, due to the hazard in handling glycide. As to the use of glycide as an oxyalkylating agent, see U. S. Patent No. 2,089,569, dated August 10, 1937, to Orthner et al.

The amount of catalyst used in oxyalkylation may vary from as little as up to 5%. The amount may vary during the oxypropylation period, as exemplified by the addition of the catalyst at the very beginning of the reaction only and with no further addition. Needless to say, there is a comparatively high concentration of catalyst at the beginning of the reaction and a comparatively low concentration at the end;

in fact, not infrequently the amount of catalyst at the end will be one-half of 1% sodium methylate, or caustic soda, or less. Catalyst can be added intermittently during the reaction period, provided suitable equipment is available. It is rather difiicult to employ such equipment on a laboratory scale, but it can be employed, of course, on a pilot plant scale or larger scale.

In the present situation, since comparatively little of the alkylene oxide was added per phenolic hydroxyl, time of reaction is not apt to be a factor. The amount of alkylene oxide may vary, for example, from one-half mole to less than two moles per phenolic hydroxyl. In other comparable oxyalkylations, as have been described in the literature, the amount of oxide added might be 50 to times this amount. Under such circumstances, it is necessary to speed up the reaction in order to finish the process within a reasonable length of time. In the present case the amount of oxide added wa= so small that even using a low-temperature (95 to C.) and a comparatively low pressure, less than 30 or 40 pounds maximum, the reaction was complete in a .very short period of time. As a con venience, I have generally added the oxide over a 13-hour period, since the apparatus was practically automatic. The amount of catalyst used was generally about 1.0% of the initial resin. Somewhat more can be used, or slightly less. If more is used the reaction would, of course, be faster, and if less is used, reaction might be a little slower. It is my preference to use a mini= mum amount of catalyst, rather than an excessive amount, for the reason that it is desirable to neutralize the excess alkalinity with hydrochloric acid, for example, or sulfuric acid, or phosphoric acid, and remove the inorganic salt prior to hydrogenation, as described in Part 3, succeeding.

One limitation of small-scale autoclave equipment (a gallon to a 2-gallon autoclave) is the difficulty involved in a suitable automatic device for adding a dry catalyst such as sodium methylate, during the reaction. This presents no problem on a large scale with larger size equipment, and thus, the same operation condwted in equipment of increased capacity means that all the catalyst need not be added at once, but can be added intermittently in a predetermined amount, based on an hourly rate, or based on the addition of ethylene or propylene oxide. For instance, in a large scale operation involving equipment having about twenty-five times the capacity of the autoclave employed, arrangements were made to introduce better than a galion of ethylene or propylene oxide (4,000 grams) per hour, along with the introduction of 20 grams of sodium methylate hourly during the operation period.

The net result, as far as the final material was concerned, was the same, to wit, a residual alkaline catalyst equivalent to about sodium methylate.

In the following example sodium methylate is used as a catalyst. The resin used was prepared in the manner described by reference to the a examples in Part 1. In practically every instance, the resin was re-prepared in a triple amount, i. e., using 3 moles of the phenol as a starting material. In each instance the amount of xylene employed was three times the amount used when only one mole of a phenol was employed, i. e., 300 grams. In all other respects, amount of aldehyde, etc.,

of illustration:

the procedure was the same, the weight ratios only being different. In the succeeding tables the amount of xylene resin solution is shown by weight; subtracting 300 in each instance gives the weight of the resin. For purpose of calculation the alkylene oxide added and the original phenol employed in manufacture was used as a basis. This was more convenient than using the weight ofresin obtained, because it may vary somewhat from batch to batch. The weight of the resin solution was such as to correspond with the original weight shown in Part 1. This is obvious by mere comparison. Actually, the amount was weighed on a laboratory balance which may have been inaccurate to the extent of 141% or This, of course, is immaterial in a procedure of the present type. Similarly, the ethylene oxide and propylene oxide were weighed as closely as possible, but here again, the variation could have been oil to 1%. 3-gram moles of the phenol were used to provide the resin. The amount of oxides employedare shown in the table. The amount of catalyst (sodium methylate) employed is also shown. In all instances, the temperature as stated, was never higher than 115 C. and generally varied from 100 to 110 C. The pressure was never higher than 40 pounds per square inch, and in all instances, the reaction was complete in three hours.

Oxyethylation or oxypropylation was conducted in the usual manner, first sweeping out the equipment with nitrogen and setting the controls as far as the addition of the oxide was concerned, but ignoring the controls as far as temperature and pressure were concerned. Any adjustment required in the matter of temperature and pressure could be made manually by examination of the gauges a few times during the entire procedure. The next step was to add the ethylene oxide or propylene oxide in such a manner that it was injected in the reaction vessel in somewhere between 2 to 2 hours, and then permitting the reaction period to extend up to 3 hours, so as to be sure all the oxide had combined. A specific example is included, following by way Example 1b 486 grams of a resin of the kind described in Example 1a 01' Patent 2,499,370 mixed with 300 grams of xylene, were used as the initial charge. To this there was added about 1% (5 grams) of sodium methylate. These ingredients were placed in the autoclave and the autoclave sealed and the automatic devices adjusted for injecting a comparatively small amount of oxide, 135 grams, in about 2% hours. The reaction was continued for a total of 3 hours, however, to be sure it was complete. This is a ratio of one mole of oxide for each initial phenolic hydroxyl involved in resin manufacture. The temperature was approximately C. and the pressure was less than 30 pounds per square inch. The final product was a viscous, semi-resinous product, being somewhat between a resin and a viscous, amber-colored fluid obtained by increased Oxyethylation. In such instances where the resins employed were liquids, needless to say, further oxyalkylation was in the direction of reduced viscosity. Some resins which were practically viscous liquids to start with became less viscous or more towards the liquid stage. The color varied from deep red or amber to some darker shades, and in some instances, lighter shades. The residual product was, of course, slightly alkaline.

For the purpose described in the next successive part each particular sample was neutralized with hydrochloric acid and then, the xylene eliminated by vacuum distillation. The resin or tacky resinous liquid, or liquids, so obtained was then dissolved in ethyl alcohol and filtered to remove any inorganic salts. The xylene-free alcohol solution was used for hydrogenation as outlined in Part 3, immediately following.

The following table illustrates a variety of suitably oxyalkylated resins. Such resins can be treated, of course, with glycide in exactly the same manner under the same conditions, with the exception that the autoclave is simply used as a reaction vessel with a condenser and without the use of pressure. However, in handling glycide I prefer to use the glass resin pot in the manner previously described. Glycide reacts very rapidly and the molecular proportions, etc., are within the limits previously specified. The resins are identified in terms of the example numbers of Patent 2,499,370.

No. of Gr. Grs. of Mols. Orig. Ratio Mol. Ex. No. Grs. Mol. Max.

Resin Phenol Oxide to Amt. of Max. Pres. Time in Ex. No. of x ETO Equiv- Catalyst Employed Temp.

'ylene Repre- Phenolic Catalyst 0 per sq. in hours Resin Solution sented by Used lent Hydroxyl Solution 111 la 786 3 3 1:1 Sodium methylate.. 5

3b In 786 3 235 5% 1%:1 6

9b 7a 870 3 235 5% 1%:1 6 10b 80 954 3 135 3 1:1 7 11b 8a 954 3 200 4% 1%:1 7 12!) 8a 954 3 235 5% 1%:1 7 13b 91; 846 3 135 3 1:1 6 14b 9a 846 3 200 4% 1%:1 6 156 9a 846 3 235 5% 1%: 1 6 16b 69!! 1,032 3 135 3 1:1 7

19b 70a 996 3 135 3 1:1 6 20b 7011 996 3 200 4% 1%:1 6 21b 7011 996 3 235 5% 1%:1 6 22b 70a 1, 038 3 135 3 1:1 7 23b 70a 1, 033 3 200 4% 1%: 1 7 24b 70a 1, 038 3 235 5% 1%:1 7 25b 730 1,122 3 135 3 1:1 8 26b 73a 1,122 3 200 4% 1%:1 8 27b 73a 1, 122 3 235 5% 1%:1 8 28b 14a 810 3 135 3 1:1 5 29b 14a 810 3 200 4% 1%:1 5 30b 810 3 235 6% 1% 5 o 1 1 1 t31" R8121 M 1 E N 2 0 S Grs. Mol. Max.

Resm Phenol Oxide to Amt. of Max. Pres. 'I1me. in N0 X lene Repre- E5311: Phenolic catalyst Employed Catalyst i s per sq. in. hours 5 So ution sented by Hydroxyl Solution 31!) 1a 786 3 175 3 1:1 Sodium Methylete 5 3l1rs. or less. 320 111 786 s 200 4% 195:1 --.-.do 5 Do. 33b 786 3 305 5% 1%:1 5 Do. 340 311 32s a 175 s 1: 5 Do, 3511 311 828 3 200 4% 115:1 0 Do. 36b 828 3 205 5% 1%:1 6 37b 7a 870 3 175 3 1:1 6 Do. 380 7a 870 3 2 50 4 195:1 0 Do. 3911 7a 870 a 505 5 & 1%:1 6 o, 40b 84 954 s 175 3 1:1 7 Do. 410 Ba 954 3 200 4% 1%:1 7 4211 a: 051 s 205 5% 1%:1 7 p0, 43b 72a 1,038 a 175 3 1:1 7 44b 720 1,038 3 250 4% 1%:1 7 D0. 450 720 1,038 3 205 5% 1%:1 7 46b 7317 1,122 3 175 3 1: 1 8 D0, 47!: 7311 1,122 a 250 4% 115:1 3 48!: 7311 1,122 a 3115 W 1%:1 8 4011 1411 810 3 175 3 1:1 5 Do, 500 1411 810 3 no 4% 1%:1 5 51b 1411 810 3 205 5% 1%:1 5 Do, 52b 2412 1,062 3 I75 3 1:1 7 DQ 53b 24 1,052 3 250 4% 114:1 7 p11 54!; 2411 1,082 a 305 5% 1%:1 7 Do. 55b 34a 2143 s 175 3 1:1 5 56b 3411 843 s 250 4% 115:1 5 p0, 57b 34a 84:; 3 305 5% 1%:1 5 D0, 580 11011 1,385 3 175 3 1:1 10 Do. 59b 8011 1,305 a 250 4 1%:1 10 Do. 500 2011 1,355 3 305 5% 1%:1 10 D PART 8 w v 'lemper- Temper- Eaample 16 Time Pressure aggro, Time Pressure oture,

The oxyalhylated resin was the one previously identified as Example 127. This product, as pre- 2293 328 23 pared, contained xylene and a small amount of m2 13 0 mm 1:820 180 basic catalyst. Enough concentrated hydrogig? gag g3 chloric acid was added to neutralize the basic 2:2 1, 2% 80 11:43 11750 170 ,1 5 1, 05 11:58 1,800 175 catalyst. As previously note..., the xylene was 8:42 1,630 100 12:07 1,830 180 removed by vacuum chshllanon at a temperature 8:47 1, e50 110 12:15 1,860 100 not in excess of 200 C. During the removal of 40 2Z2? 1: F 28 g3 382 the xylene, the water ntroduced by the addition 9:01 1,750 135 12:39 1.1130 105 of a small amount of hydrochloric acid was also 8;{8 {42g 1' gig eliminated together with any small excess of 3 1:1 1,238 3 20 hydrochloric acid, which may have been present. 800 150 m 750 This residual mammal was then dissolved in 300 85%? 3 3 128 grams of ethyl alcohol, 1. e., an amount equal to 10307 1:810 160 11700 230 the xylene originally present. The anhydrous 1014 1,800 165 0 ,690 240' ethyl alcohol solution was allowed to stand for i three days and then filtered so as to remove a The next morning, after Standing e ght, small amount of precipitate. The amount of the temperature had pp C- a he solution at this time was substantially the same as at the end of the previous operation, to wit, approximately 921 grams, of which 300 grams represented solvent. This was hydrogenated in two substantially equal half portions. Approximately 460 grams of the material described were placed in an autoclave along with 31 grams of Raney nickel. The amount of Fancy nickel used in all instances was approximately 10%, by weight, of oxyalkylated reaction calculated on a solvent-free basis.

The apparatus employed was a stirring type super-pressure autoclave manufactured by the American Instrument Co., Silver Spring, Maryland, and described in their Catalogue No. 406 as the 4%" series. The instrument was, of course, equipped with all the conventional fittings. The stirring speed employed was approximately 450 R. P. M. The following table shows the time required to hydrogenate. The initial time period shows the starting period in the morning and the second and third columns show the gauge pressure in pounds per square inch and the temperature in degrees centigrade:

pressure to about 835 pounds. The material was then removed by draining the autoclave and then washing with approximately 400 to 500 grams of anhydrous isopropyl alcohol. The mixture of alcohols was then removed by vacuum distillation at less than C. The hydrogenated product was substantially identical in color as prior to hydrogenation, although there may have been some bleaching effect during the hydrogenation reaction. The solubility of the material was not particularly changed in comparison to the product prior to hydrogenation. The tests for aromatic character, such as decolorization of bromine water, indicated that the product was entirely, or nearly entirely, converted into a hydroaromatic compound.

Similar hydrogenation was conducted in which no alcohol was employed as a solvent, the resin having been added to the autoclave in a powdered form, and in such procedure the temperature of the autoclave was raised to C. before starting to introduce hydrogen. The hydrogen was introduced cautiously, being careful to see that the pressure did not go past 1900 pounds and that the temperature did not get past 235 C. The

presence or absence of alcohol did not seem to v matter particularly, as it was merely a choice with regard to convenience. Other alcohols can be used, such as methyl, propyl, etc. Such alcohols, of course, do cause some increase in pressure, particularly at the higher operating temperatures.

The same procedure was carried out in regard to all the various oxyalkylated products described in Part 2, preceding. The following table shows the example number correspondence between the oxyethylated non-hydrogenated material and the derivative obtained by hydrogenation, together with the maximum temperature, pressure, and time employed to hydrogenation. In each instance the amount of catalyst employed (Raney nickel) was approximately 10% of the solventfree powder. In some instances, low molal alcohols were employed as solvents, and in other instances, no solvent was present. Actually, the hydrogenation procedure, using Raney nickel and equipment of the kind now available is comparatively simple.

In the matter of hydrogenated phenol-aldehyde resins, see U. S. Patents Nos. 2,072,142 and 2,072,143, both dated March 2, 1937, and both to Ubben.

Ex. No. of Max. Pres.. Time of Hydro- 3 f g lbs. per Hydrogenated g srvuare genation,

Derivative ate esm inch hours 10 1b 240 1,870 6% 20 2b 250 1, 830 6 36 3b 260 1, 790 46 4b 245 1, 815 6% 5C 517 250 1, 890 6 66 6b 260 1, 835 5 7L 7b 240 1, 795 5% 86 8b 235 1,800 6% 9c 9b 230 1, 730 6% 10C 1011 250 1, 725 5% 11C 1117 245 1, 750 5% 12C 120 240 1, 725 7 13! 13b 240 1, 800 6% 14C 14b 230 1, 825 6% 15C 15) 235 1, 830 7% 16C 16b 245 1, 850 7 17C 17b 255 1, 790 6% 18C 18!) 250 1, 820 5% 19!! 19b 260 1, 890 5% 20C 20b 255 1, 835 5% 21C 21!) 245 1, 820 6% 22C 2217 240 1, 815 7% 23C 23!) 240 1, 850 7 24C 2417 235 1, 825 6% 25C 25!) 235 1, 830 8 26C 26!) 250 1, 750 7% 27!! 27') 255 1, 765 7% 28 280 245 1, 765 6% 29!: 29!) 240 1, 780 5% 30C 300 260 1, 890 6 31C 31b 266 1, 800 6% 320 32b 235 1, 805 11% 33C 33!) 255 1, 790 7 340 34 255 1, 780 7% 35!: 35b 240 1, 725 6% 36C 36b 240 1, 725 6 37C 371) 235 I 1, 830 5% 38C 38b 245 1, 820 6% 39C 3917 260 1, 880 6% 40C 40!) 230 1, 795 7 41!! 410 250 1, 725 7 /2 426 42b 240 1, 800 7% 43C 43 245 l, 790 5% 44C 44!? 260 1, 820 6% 45!! 451) 265 1, 835 5 46C 46!) 250 1, 850 5% 47 47 255 1, B15 6 48C 48D 240 1, 790 6% 49 49b 230 1, 750 6% 50C 50b 260 1, 890 5% 51C 51b 240 1, 850 7% 520 520 245 1, 730 7 53C 530 240 l, 865 6% 54C 54!) 255 1, 770 7% 55C 55b 235 1, 840 5 56 56!) 230 1, 890 5% 57C 57b 255 1, 755 6% 58C 58) 255 1, 835 6% 59C 59b 240 1, B60 7% 60 60!) 250 1, 820 7% 61C 61b 250 1, 850 8% 62C 62b 240 1, 795 8 14 sult of hydrogenation, attention is directed to what has been said preceding. Hydrogenation in numerous cases does show some bleaching effect.

The hydrogenated product freed from solvent which would be susceptible to reaction with glycidyl allyl ether, was admixed with approximately 300 grams of xylene and approximately 1% of sodium methylate. Needless to say, the alcohol employed as a solvent, and for that matter, the xylene employed in Part 1 as a solvent, could be replaced by a solvent, which would not be objectionable either from a standpoint of hydrogenation or oxyalkylation, as, for example, decalin. Again, as has been pointed out, all the reactions involved can be conducted in absence of any solvent. This is purely a matter of convemence.

In noting the size of the batch subjected to reaction with allyl glycidyl ether, no account is taken for increase in weight, due to hydrogenation, for the reason that this is a comparatively small factor, and there have been some losses in filtering, and otherwise. Therefore, the figures that appear in the next part, i. e., Part 4, corre- As to change in. physical appearance, as a re- 76 spond in essence to the figures appearing in Table II, which show the grams of xylene solution, plus the oxide added. Actually, the treatment with allyl glycidyl ether, as previously noted, is an oxyalkylation process, and the reaction is conducted in the same manner as previously men-- tioned and is substantially the same as one would conventionally employ in the use of glycide.

PART 4 As previously indicated, the present part is concerned with the reaction between allyl g1 cidyl ether and the alicyclic compounds obtained in the manner described in Part 3, immediately preceding. Such alicyclic compounds are polyhydroxylated, having at least three or more hydroxyl radicals per molecule. Generally speaking, the number of hydroxyl radicals, if obtained by the reaction of ethylene oxide or propylene oxide, for example, would run from 3 to 7 or 8, unless the resin, prior to hydrogenation, had been treated in such a manner as to have present a greater number of phenolic hydroxyls, such as a condensation reaction to increase the resin molecule size. Obviously, if glycide or methyl glycide were used, the number of hydroxyl radicals would be substantially larger, for instance, 10, 15, 20, or even more. In any event, the amount of allyl glycidyl ether employed is suflicient to convert at least a plurality of hydroxyl radicals per molecule into the corresponding allyl compound and may be enough to convert all hydroxyls present, or two or three times this molal amount. More allyl glycidyl ether can be employed than corresponds to the molal proportion, based on hydroxyl radicals present, for the simple reason that at each stage of reaction a hydroxyl is obtained, which, in turn, is susceptible to further oxyalkylation with any alkylene oxide, and of course, with allyl glycidyl ether.

The use of allyl glycidyl ether, as previously noted, involves substantially thesame procedure and equipment as glycide. The glass equipment, previously described could be used, although I have found it more convenient to employ the larger laboratory autoclave previously described. The use will be illustrated by the following examples. I

As to further information in regard to allyl glycidyl ether, see Information Sheet DS-48-22 of Shell Development 00., Emeryville, California.

Example 1d The same piece of equipment was employed as previously described in Part 2, i. e., an autoclave, although in the instant procedure involving the 16 ture for the addition of the oxide was controlled within the range of 115 to 135 C. The reaction took place at atmospheric pressure, with simply a small stream of nitrogen passing into use of allyl glycidyl ether, there was no pressure the autoclave at the Very top, and Passing out involved and certain changes were made, as noted of the open condenser 50 as avoid y D subsequent1y The autoclave was equipped with sible entrance of air. Under such operation there a water-cooled condenser, which was shut oil? w of course some 1055 of Xylene, but examine:- when used as an autoclave. It was equipped also revealed no loss the oxidewith a separatory funnel, and an equalizing pres- The product Qbtamed was fiuld lighter in sure tube, so the liquid such as allyl glyeidyl color than the initial example, and on examiether, could be fed continuously at a drop-wise natlonr was f?und be (fomparatively free from or faster rate into the vessel, and the rate w unrescted 0 de. Llkewise, examinatron by decontrolled by visual examination. For conventermlnatlon 01 he hydroxyl number showedsubience, this piece of equipment is efer ed to as stantial completeness of reaction. Needless to an autoclave, because it is essentially designed say, such procedure also increased the water solufor such use, but it is to be noted it is not so used when allyl glycidyl ether, or for that mat- 15 s 111 W instance in regard D ter, glycidyl, was employed, a described i t cal properties applies for all practical purposes 2, preceding to all examples obtained. Obviously, where in- There were charged into the autoclave 921 creased amounts of the ether were employed, the grams of a xylene solution (containing 300 grams final P F P tended showmore and more the of Xylene) id ntified as Examme 1 preceding characteristlcsof a VlSCOllS liquid comparable to s amount f sodium methylate equivalent to castor 011 or slightly blown castor oil. The color about 1% of the hydroxylated reactant, w also decreased as more ox1de was added, added as a catalyst, which, in this instance, was Example 2d 6.5 grams. The autoclave was sealed, swept with nitrogen gas and stirring started and heat ap- T1116 saime w employed as m E plied immediately. The temperature was alampe precedlng, usmg the same operatmg lowed to rise to The anyl glycidyl ether procedure and substa ntially the same temperaemployed was the technically pure product suprange wlth thls dtfierencei P u plied by t Shell Development Co" Emeryvine, sub ected to treatment with allyl glycidyl ether canfornia was the hydroxylated compound identified as x- Ihe hydroxylated reactant present in the autoample 2c: precedmg- The a employed in Cleve represented approximately 3 moles of the instance was 986 grams, including 300 grams nol when calculated back to the initial reactants of solvent The amount of sod-111m methylate used described in Part 1. The amount of allyl glycidyl as a catalyst was 7 /2 grams In all other respects ether added was approximately 3 moles or the Operating procedure Was identical the grams. This was added over a 3 /2 hour period. two precsdmg sXalPples- This was charged into the upper reservoir vessel operatnig data 1n regard to s examples which had been flushed out previously with 111- are v n n e tables imm ly foll win trogen, and was, in essence, the equivalent of lncldentally, It is to b note that one need a separatory funnel. The oxide was started not se sodium methylate as a Catalyst. ut a slowly into the reaction mass at a drop-wise rate. use any 0118 O a number Of ot er u table cata- The reaction started immediately and the temlysts, such as caustic soda or caustic potash. perature rose approximately 13 to 19. Cooling Stannic chloride or boron fluoride ether complex water was run through the coils so the temperaare also satisfactory.

E N 1 131 i fi l x i i 0 Ex. 15110 3112 oou fg u rid solvent Amt, Catalyst Amt, 23 each M01: g- 2 93? Timaol N0 an as:

Oaea basis), grs. present 1a lo 621 350 1:1 Not over 138.. 11V 211 2c ass 350 1:1 do 2% 3a 3c 721 350 1:1 2 ,5 4d 10 789 350 1:1 4 5a 854 350 1:1 3% 6d 889 350 1:1 3% 771 867 350 1:1 3 8d 18c 932 350 1:1 2% 9d 19: 967 550 111 4 10d 250 957 350 1:1 4 1111 260 1, 022 350 1 :1 1m, 12d 27 1, 057 350 1 :1 3% 13d lo 621 260 3:4 2%, 14a 20 686 260 3:4 2% 15a 30 721 260 3:4 2 1611 100 789 260 3:4 3 1711 110 854 260 3:4 3% 18d 12c 889 260 3:4 4% 19a 170 867 260 3:4 4 20d 932 260 3:4 4% 21a 967 260 a 4 3% 22d 251 957 260 3:4 4 23d 260 1, 022 260 a: 4 4% 24d 27 1, 057 260 a: 4 3% 25d 37c 745 350 1:1 3% 2611 386 830 350 1:1 4 27d 39: 875 350 1:1 3% 28d 490 685 350 1:1 3 2911 50c 770 350 1:1 3% 30d 51c 815 550 1:1 2%

Attention is again directed to the fact that other suitable solvents other than xylene may be used, such as decalin, cymene, etc. Other suitable catalysts can be employed. It is also pointed out that the amount of allyl glycidyl ether employed need be only enough to introduce a plurality of allyl radicals per resin molecule, or may be enough to introduce a number of allyl radicals equal to the original phenolic hydroxyls, or twice as many, or three times as many. My preferred ratio is to use 3 moles of allyl glycidyl ether for each 4 moles of phenol originally used, or to use an equal number of moles, 4 for 4, or else, 5 moles of allyl glycidyl ether for each 4 moles of phenol originally used.

PART 5 The allyl-radical-containing products are polyinerized in much the same way as comparable products, for instance, castor oil, dehydrated castor oil, allyl sucrose, or the like, are polymerized or thickened or bodied. Such polymerization is due essentially to the allyl groups undergoing allyl or vinyl condensation, or polymerization. Such vinyl polymerization is usually induced by use of a peroxide catalyst, such as benzoyl peroxide or blowing with a gaseous oxygen-containing medium, or by using a combination of the two procedures.

In any event, the usual steps are taken to free the compound from any solvent, such as xylene, which may be present and also to render it as nearly neutral as possible and to remove any inorganic salts which would tend to separate out. A slight basicity, due to the presence of a basic tertiary amine is desirable in connection with with the use of a peroxide. This applies whether the peroxide is used for partial polymerization, followed by blowing with air, for example, or is responsible totally for the polymerization. This practice, 1. e., the use of a tertiary amine to act as an activator in peroxide, for instance, benzoyl peroxide, to induce polymerization is well known.

Tin chloride seems to have similar properties, but is not as satisfactory. For a number of reasons, oxidation by means of air alone seems to be the simplest and the most satisfactory procedure.

Briefly stated then, the various products identified as Examples 1d through 30d in Part 4, preceding, are neutralized with sufiicient concentrated hydrochloric acid to make them neutral. Any sodium chloride formed is removed by filter ing. The product is then subjected to vacuum distillation which removes the xylene used as a solvent and also any water formed during the neutralization step. The final product varies from a semi-viscous liquid to a viscous or tacky liquid, or a product which exhibits almost a solid state at ordinary temperature. In all instances these products are fluid at the temperature employed for polymerization, for instance, 110 to 150 C. Previous reference has been made to the fact that polymerization with air is comparable to the procedure that is used in obtaining an oxidized oil or blown oil, or a polymerized castor oil from castor oil or similar materials, as, for example, allyl sucrose. Such products are produced by the common practice of blowing or oxidizing the polymerizable material by means of a gaseous medium, such as air, oxygen, ozone, or ozonized air. The gaseous medium, such as air, may be moist or dry and the oxidation, or better still, polymerization, may take place in presence or absence of a catalyst. The catalyst may be of a metallic type, such as lead rlcinoleate,

cobalt ricinoleate, manganese riclnoleate, etc., or it may be or an organic type which produces a peroxide, such as alpna pinene, linseed ou, etc. Similarly, as previously noted, peroxides tnemseives, such as benzoyl peroxide, or similar peroxides, may be employed as catalysts, or to inhibit the incipient stage of polymerization. Such peroxide catalyst may be used in presence of a basic tertiary amine, as previously noted. The amount of catalyst may vary from as little as one-tenth of 1%, to 1%, or somewhat less. The amount of tertiary amine employed in connection with the peroxide, is usually in approximately the same order of magnitude, 1. e., one-tenth of 1%, up to 1%. Examples of such tertiary amines include trlbutylamine, triamylamine, tricyclohexylamine, etc.

Polymerization can be induced by oxidation at atmospheric pressures, or super atmospheric pressures, i. e., pressures up to or including 200 pounds gauge pressure, and at temperatures from slightly above the boiling point of water, up to any temperature that does not produce undue decomposition by pyrolytic reaction.

The time of polymerization, as induced by blowing or oxidation, may be fairly brief, for example, less than 25 hours, particularly if such oxidation takes place in conjunction with the use of a peroxide, such as acetyl peroxide, or benzoyl peroxide. On the other hand, in some instances, using a temperature of approximately C., it is sometimes necessary to blow the mixture for as long as 125 to hours.

Not infrequently there is a change in the index of refraction of products during the polymerization stage. In other words, as the allyl radicals disappear, due to polymerization, there is an increase in the index of refraction. Under any particular set of conditions a study of such index of refraction may be helpful in controlling the polymerization, although as a rule, viscosity is equally satisfactory, insofar that no effort is made to reach an exact quantitative point in the polymerization range. Generally speaking, I have attempted to prepare compounds having at least three different degrees of polymerization. One stage is where there has been a noticeable increase in viscosity, and the difference is substantially comparable to the difierence between heavily blown castor oil and ordinary castor oil; the second stage is the point where the product begins to show incipient stringiness. This is probably where incipient gelation or cross-linking starts to take place. The third stage is where stringiness is not only obvious but a solution of the polymerized solution in xylene, for instance, a 50% solution, still shows stringiness, but is still soluble. It is to be noted that the ultimate product, whether below the stringy stage, or in the incipient stringy stage, or at the stage where even a 50% solution in xylene is stringy, must be soluble in an organic solvent, such as xylene, low molal alcohols, decalin, diethylether of ethylene glycol, cyclohexanal, or the like. If the product is not soluble in any one of the common hydrocarbon or oxygenated solvents it is not satisfactory for the herein described process.

Polymerization is illustrated by the following examples:

Example 1e A product of the kind identified as Example 111 in Part 4, preceding, was freed from inorganic solvents and salts. The product was substantial- 1y neutral. 1500 gram of the product were placed in an ordinary 3-liter flask. The air terminal inlet was provided with a device which gave a multiplicity of small, fine bubbles. This was accomplished by means of a porous ceramic tube fitted to glass and available from various laboratory supply houses. The input of air was such that there was a continuous stream of air passing through the reaction mass sufficient to provide at least moderate agitation. The temperature was raised to 138 C., and then air was 7 passed through for 117 hours. During approximately the first third of the period, i. e., for the first 40 hours, there did not seem to be any particular change.

During the second 40 hours the material began to darken and was almost blackish-red at the end of 80 hours. By this time there was a modest but appreciable change in viscosity, even though not so marked as at the end of the final reaction period. Viscosity, of course. could not be judged satisfactorily when the material was hot, but when the reaction mas was allowed to cool and the viscosity compared with that of the initial reaction mass at the same temperature, for instance, room temperature, it was obvious that a thickening, somewhat suggestive of the change that takes place when castor oil is converted into a light blown castor oil, had taken place.

At the end of the final period the viscosity of the product had greatly increased and was suggestive of that of heavily blown castor oil. The initial product showed a viscosity more comparable to ordinary castor oil. This product was considered a characteristic as being the result of mild blowing or mild polymerization. Note what is said in regard to such characterization in subsequent Example 'le.

Example 2e The same procedure was followed in every way as in Example 1e, except that the initial charge was 1500 grams of a product identified as Example 2d in Part 4, preceding. The temperature of polymerization, the time period, the change in the product, change in color, final viscosity, etc., were substantially comparable to Example 1e, preceding.

Example 3e The same procedure was followed in every way as in Example 1e, except that the initial charge was 1500 grams of a product identified as Example 3d in Part 4, preceding. The temperature of polymerization, the time period, the change in the product, change in color, final viscosity, etc., were substantially comparable to Example 1e, preceding.

Example 4e The same procedure was followed in every way as in Example 1e, except that the initial charge was 1500 grams of a product identified as Example 28a in Part 4, preceding. The temperature of polymerization, the time period, the change in the product, change in color, final viscosity, etc., were substantially comparable to Example le, preceding.

, Example 5e The same procedure was followed in every way as in Example 1e, except that the initial charge was 1500 grams of a product identified as Example 29d, in Part 4, preceding. The tempera- 20 ture of polymerization, the time period, the change in the product, change in color, final viscosity, etc., were substantially comparable to Example le, preceding.

Example 6e The same procedure was followed in every way as in the Example 1e, except that the initial charge was 1500 grams of a product identified as Example 30d, in Part 4, preceding. The temperature of polymerization, the time period, the change in the product, change in color, final viscosity, etc., were substantially comparable to Example 1e, preceding.

Example ?e The same procedure was employed as in Examples 1e through 6e, preceding, except that a stirring device was included in the reaction fiasl: along with the distributing unit. In this case the temperature was held at slightly less than in the previous six examples, i. e., at about 136 C. The stirring device apparently gave better oxidation, which, in turn, resulted in more effective polymerization. At the end of the hours the product was not only stringy, but when mixed with an equal weight of xylene, the 50% xylene solution so obtained showed stringiness. In fact, the product, prior to dilution in xylene, was even more than stringyit was somewhat rubbery. I have characterized the product which is blown just short of the rubbery or stringy stage, as exemplified by Examples 1e to 6e, preceding, as being mildly oxidized or mildly blown, or mildly polymerized.

I have used the expression drasticallyoxidized to indicate a product which is not only stringy or rubbery as such, but also is highly viscous and shows stringiness or rubberiness in the 50% xylene solution. Such stage is typified by the present example, i. e., Example 7e.

Examples 8e to 12e The same procedure, i. e., the production of a drastically polymerized product was applied to Examples 2d, 3d, 28d, 29d, and 30d, in the same manner as described in Examples 2e through 6e, inclusive, except that the stirring device was used in each instance and in no case was a temperature higher than 140 C. employed. In each instance the final products were dark, stringy, or almost rubbery and showed stringiness or rubberiness in a 50% solution of xylene.

Example 13c The same procedure was employed in every respect as in Examples 1e, through 7e, preceding, and the particular procedure employed was the use of the stirring device, as described in Example le. The initial charge as before was 1500 grams of the product identified as Example 1d. The temperature of polymerization was again within the range of to C.

In this example, and in the subsequent five examples, the time period was less than in Examples 7e to 12c, inclusive. In the instant example it was 82 hours. This product at the end of this period showed a definite tendency to string or rubberize, but this property practically disapp ared when a 50% solution in xylene was prepared. I have referred to this particular stage as being semi-drastically oxidized to indicate a product which shows incipient stringiness, as such, but where such stringiness disappears on dilution, as previously noted Examples 132 to 18c, inclusive The same procedure was followed as in Example 13e, preceding, i. e., a procedure employed so as to produce a semi-drastically polymerized product and the products subjected to polymerization were thus identified as Examples 2d, 3d, 2801, 29d, and 30d, in Part 4, preceding.

Actually blowing or polymerizing can be conducted with ozone or ozonized air, as well as air which may or may not have its moisture content eliminated. In this particular type of reaction I have found no advantage in going to any added cost in regard to the oxygenating procedure which initiates polymerization.

The same is true of a cataylst, such as lead, manganese or cobalt naphthenate or the like as has been described in the literature previously mentioned. Such catalyst in comparatively small amounts, one-tenth per cent or preferably less, will speed up the polymerization, but here again I have not found this particularly desirable. Since it is usually intended to stop the polymerization at some particular point by use of a mild blowing or a semi-drastic blowing, or a drastic blowing, it is of greater convenience to approach the end point slowly, rather than rapidly, and also to have polymerization cease when the air stream stops.

As I have pointed out previously, the period of oxidation can be controlled in various ways; for instance, a higher temperature can be used, or more air will be forced through the mass; more violent agitation can be employed; and most im portant of all, if desired, one can shorten the socalled incubation period by use of a peroxide alone, or a peroxide in combination with a tertiary amine. My experience indicates that in many instances there are present materials which appear to inhibit the polymerization step, possibly a trace of phenolic compounds. Oxidation appears to counteract or destroy these products slowly, and then an incubation period seems to develop where peroxide, or the like, is built up. After this stage, polymerization takes place comparatively rapidly. This conforms to the pattern of other comparable polymerizations involving allyl compounds. I have been able to cut PART 6 The polymerized derivatives of the kind described in Part 5, immediately preceding, were subjected to oxyalkylation by means of the variousalkylene oxides previously described. The

equipment used and the procedure were the same as described in Part 2, preceding, except in the following respect: In Part 2, preceding, the amount of alkylene oxide added per initial reactant, i. e., the product being subjected to oxyalkylation, was comparatively small. The amount of alkyleneoxide was in the neighborhood of one to two moles per phenolic hydroxyl. For this reason the reaction period was comparatively short, regardless of whether high temperature or low temperature oxyalkylation was used. The expression high temperature refers to oxyalkylation taking 'place at 150 to 200 C., or, in some'instanoes, somewhat higher. The expression low temperature oxyalkylation refers to temperature approximately that of the boiling point of water, for instance, to C., with to C. as average, and perhaps as high as C. at times. Suitable equipment is used to'control the time period involved, i. e., the speed down the time required in preparation of products characterized by Examples 1e through 18c, preceding, by doing nothing more than adding about 4% of benzoyl peroxide and blowing until incipient viscosity change takes place. If this did not appear in the first ten hours, I then added a second equal portion of benzoyl peroxide and repeated. 'Usually, the first addition of benzoyl peroxide or' a slightly larger amount was suflicient. an addition of a third portion of benzoyl peroxide, but is has been exceptional that this has been required. Actually, all the various stages of polymerization can be obtained by use of a peroxide induced polymerization in a fourth or a third or in one-half the time required by air alone.

The final products obtained by these procedures varied from heavily viscous liquids to-semi-rubbery or almost rubbery, or in fact, rubbery solids or semi-solids, which, in each and every instance, were soluble in an organic solvent, as previously described. Needless to say, oxidation can be conducted in any convenient size reaction vessel; in

In some instances I have made i of injecting the oxide, and also the maximum temperature, the maximum pressure, etc. In Part 2, in order to use a comparatively low temperature (110 to.120'C.), two additional contro units were connected to the equipment.

i'In the' present oxyalkylation process, the amount of alkylene oxide being added is comparatively large, for instance, an equal weight or twice the weight, three times the weight, several times the weight, or even more, based on the initial reactant. For this reason, the higher temperatures were employed and the low temperature controls previously referred to in Part 2 were disconnected. The process is comparatively simple; the polymer, either as such as diluted with xylene or other suitable solvent, if desired, is placed in the autoclave along with a suitable amount of alkaline catalyst usually sodium methylate. The equipment is flushed out with nitrogen, various controls set, and oxylalkylation proceeds in the conventional manner. The procedure will be illustrated by the following examples.

Example 1 500 grams of the polymer identified as Example 1e, preceding, were mixed with 500 grams of xylene and 10 grams of sodium methylate. The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc.-, which are conventional in this type of apparatus. The capacity of the autoclave was approximately 3 liters. The stirrer was operated at approximately 30 B. P. M. There was charged into the autoclave the mixture previously referred to, i. e., the polymer, the solvent, and the catalyst. The autoclave was sealed, swept with nitrogen gas, and stirring started immediately and heat applied. The tem-' perature was allowed to rise to approximately C. The automatic controls were set to stop the reaction at C. and also to stop the equipment in event the pressure got higher than 200 pounds per square inch. The amount of ethylene oxide added was 500 grams. The inlet speed was set so as to introduce this amount of oxide in 2 hours. The injection of the ethylene oxide was controlled so it would all be added in one hour's time. An allowance was made for the fact 24 use propylene oxide in combination with either ethylene oxide or glycide, or both. It is understood that water-solubility may be particularly desirable to produce a surface-active agent, but

pylene oxide were used to replace each grams of ethylene oxide. Propylene oxide did not pro duce equivalent water-solubility, even at the ultimate stages, or even when used in a greater amount. For this reason, it is my preference to that the pressure control or temperature con- 5 water-solubility is not necessarily the criterion of trol might stop the injection of ethylene oxide an effective demulsifier. Indeed, some of the at various intervals during the addition of the water-insoluble compounds obtained with prooxide, and for this reason a 2-hour time period pylene oxide appear to be as good demulsifiers was allowed for actual injection of the oxide, i. e., as the more water-soluble ones obtained in a mixinjection at the rate of 500 grams per hour, plus 1 ture of alkylene oxide, as described in the next an added interruption period of an hour, plus a succeeding paragraph. half-hour for stirring at the end of the reaction. In one modification the procedure followed In actual operation the oxide was added in sllghtwas the same as in Examples 1) through 21), but 1y over an hour, and the final period of stirring with this difierence; in the first two stages of probably was considerably over an hour. T is, oxyalkylation the amount of ethylene oxide indiof course, was purely a matter of convenience and cated was replaced by 32 more of propylene immaterial for the reason that if the temperaoxide. In some instances the time required for ture had been IB-lSBd1 slightly, or the amount of oxypropylation was somewhat longer than for catalyst increased, the reaction could have taken oxyethylation, and in some instances, the templace in evenashorter period of time, for instance, 2 perature was slightly higher, 5 C. to 12 C., for 45 minutes. N0 h w e 0 example. The former insoluble product after the e te dl the p d f reeetlon. a d likewise. second stage of oxypropylation was then treated no h f done In havmg a longer St i with ethylene oxide in the same manner noted period during the c i o in ure th re wa in the previous table. If the product did not no rac of y e Oxide left. During s time happen to be water-soluble, or sufiiciently watert e temperature did reach um po soluble, a fourth oxypropylation was employed, 1. e., 165 but the pressure d1d not go higher than using ab t 25% of th t, of ethylene 170 pounds per square inch. ide previously noted. This second addition of resultant p d t was a light amber oil ethylene oxide and four oxyalkylation invariably which d sper reedlly 1n Wete! either in pfesproduced water-solubility. Note what has been enee 0f y e, 9 after the Xylene Y IemOVedsaid previously that water-solubility per se is not is e y y i Product Was subleeted be a criterion of effective demulsifying action. It the! Xyethy1at1n m the Same manner as noted does, however, frequently characterize a waterin the n ns table under p e soluble surface-active material suitable for pur- The example 1dent1fied as 20 in the table was poses other than demu1sifi ati then subjected to a third stage of oxyethylation, as noted under Example 3c in the table. Various Example 23f other oxyethylations were conducted. in the same manner under substantially the same operating The same piece of equipment was used as preconditions. Such data are recorded in the table viously described, i. e., an autoclave, although in immediately following. the instant experiment involving the use of gly- 1) "I li i l u 'i ETC '1 ll 1: 9 a resell 8 Y Time Pres Solubility he... is? raid, the em 55.9.2. me

free) lenc) Grms. byWeight if 16 500 500 10 500 3 165 170 1:1 Emuls. or sol. 2} 1f 1,000 500 5 no 4 178 145 2:1 11101. sol. 3f 2/ l, 510 500 6 530 4 180 170 3:1 Excel. 4f 22 505 510 11 505 3% l 185 1:1 Emuls. or so]. 5] 4f 1, 010 510 5 520 3% 175 170 2:1 Increased. 6f 5] 1, 530 510 1 500 1 185 160 3:1 Excel. s017 7] 3a 495 485 10 520 4 155 150 1:1 Emuls. 0r sol. 8] 71' l, 015 485 4 510 4 164 150 2:1 Incr. so]. 9/ 8f 1, 525 485 5 490 3 169 150 3:1 Excel. 501. 10! 78 503 498 12 495 3 150 160 1:1 Emuls. or sol. III 101 99s 49s 5 490 a 151 180 2:1 11101.501. 12; 11 1,488 492 5 525 4% 158 175 3:1 Excel.sol. 13f 13c 500 510 9 490 3 185 165 1:1 Emuls. or sol. i4] 13] 990 510 5 520 a 2:1 Incr.s0l. 15; 14 1, 510 510 a 540 1 165 135 3:1 ExceLsol. 16f 5e 505 515 10 515 4 166 170 1:1 Emuls. or Sol. 17] 16] l. 020 515 7 600 41/2 165 2:1 incr. sol. 18f 17f l, 520 515 5 505 3 180 150 3:1 Excel. so]. 19) 6: 520 505 10 510 3% 145 1:1 Emuls. or sol. 20] 19/ 1,030 505 6 490 456 155 170 2:1 Incr. so]. 21 20] 1,520 505 5 520 4 130 3:1 ExceLsol.

Example 221 cide there was no pressure involved and certain Propylene Oxide was used instead of ethylene 65 changes were made, as noted subsequently. The oxide, following the Same procedure as in autoclave was equ1pped with a water-cooled conamples e through 21f, preceding but with this denser, which was shut off when used as an autoparticular change; the amount of propylene oxclave- It was also @Q Wlth Separator? me added was reversed roughly in molar funnel and an equalizing pressure tube, so that portion, i. e., approximately 13% grams of pr 70 liquid, such as glycide, could be fed contmuously at a drop-wise or a faster rate into the vessel and the rate was controlled by visual examination. For convenience, this piece of equipment is referred to as an autoclave, because it was designed essentially for such use, but it is to be 25 noted it was not so used when glycide was employed as an alkylene oxide.

There were charged into the autoclave the same reactants (intermediate, solvent, and sodium methylate) as in Example 1f. The autoclave was sealed, swept with nitrogen gas and stirring started immediately and heat applied. The temperature was allowed to rise to 118 C. The glycide employed was comparatively pure. 360 grams of glycide were used. This was charged into the upper reservoir vessel which had been previously flushed out with nitrogen and was the equivalent of a separatory funnel. The glycide was started slowly into the reaction mass in a dropwise stream. The reaction started to take place immediately and the temperature rose approximately to Cooling water was run through the coils so that the temperature for addition of glycide was controlled within the range roughly of 110 to 130 C. The addition was continuous within the limitations and all the glycide was added in less than 7 hours. This reaction took place at atmospheric pressure with simply a small stream of nitrogen passing into the autoclave at the very top and passing out through the open condenser, so as to avoid any possible entrance of air. This amount of glycide gave the product reasonably good solubility. However, a second addition of glycide was made without adding more catalyst. The amount added the second time was 130 grams. This was added the same way in approximately a 3-hour period. This product showed moderately increased solubility over the previous sample. A third addition of oxide was made after first introducing an additional 5 grams of sodium methylate as catalyst. The third addition consisted of 250 grams of glycide. The product showed excellent solubility and excellent surface-active characteristics after the third addition of glycide. Note what has been said previously that water-solubility per se is not necessarily in index as to demulsification characteristics.

Oxyalkylated derivatives can be obtained without the use of a solvent as a diluent. This is purely a matter of convenience. Whichever solvent is used, such as xylene, cymene, decalin, or the like, can be removed by distillation, and particularly vacuum distillation. For many purposes, such as ior use in demulsifiers, the solvent can remain.

It is my preference, particularly for purpose of demulsification, to use an oxyalkylated derivative which is surface-active by a simple emulsification test intended to produce a xylene-water r.-

emulsion. A suitable procedure is as follows: The oxyalkylated product is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufiicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions, so produced, are usu-- ally xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution, and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further 26 formaldehyde), using an acid catalyst, and then followed by oxyalkyiation, using 2 moles of ethylene oxide to each phenolic hydroxyl, is helpful. Such resin, prior to oxyalkylation, has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the oxyalkylated product may not be sufiiciently soluble in xylene alone, but may require the addition of some ethylene glycol diethylether, as described elsewhere. It is understood that such mixture, or any other similar mixture, is consideredthe equivalent of xylene for the purpose of this test.

In many cases there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the products used in-accordance with this invention. They dissolve or dis-' perse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a product is capable oi. producing a dispersion in water, is proof that it is distinctly hydrophile. In doubtful cases comparison can be made with the butyl-phenol-formaldehyde resin analogue, wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus. For more complete description of this test, see U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote et al.

. The presence of xylene or an equivalent water insoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsiflcation begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas, in presence of xylene, such properties would not be noted. In

other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification, or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water, even in the presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines. In summary then, for all practical purposes emulsions, detergents'hgricultural sprays, further.

reaction with chemical compounds reactive towards hydroxyl radicals, etc.

Specifically, then, the use of such oxyalkylated derivatives is not limited to the resolution of Having thus described my invention, what I 27 claim as new and desire to secure by Letters Patent is:

1. The process of (a) subjecting an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols 1 of functionality greater than two; said phenol being of the formula:

i r i which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in one of the positions ortho and para to oxyalkylation with an alpha-beta alkylene oxide having not more than 4 carbon atoms and'selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide,.

glycide and methylglycide; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula R10, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals; with the proviso that from about one-half to less than two moles of alkylene oxide be introduced for each phenolic nucleus; b) converting said oxyalkylated resin into the corresponding alicyclic compound by hydrogenation in presence of a hydrogenating catalyst; (c) reacting said hydroaromatic compound with allyl glycidyl ether, with the proviso that at least 2 moles of allyl glycidyl ether be reacted for each alicyclic molecule and not in excess of three times the number of hydroxyl radicals present in said molecule; (d) polymerizing said allyl radicalcontaining derivative to yield an organic solvent-soluble product; and (e) subjecting said aforementioned polymer to oxyethylation with (I) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; said oxyallcylated resin being characterized by the introduction into the resin molecule at hydroxyl groups, of a plurality of divalent radicals having the formula (R), in which R1 is a'member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals,

hydroxylpropylene radicals, and hydroxybutylene radicals.

2. The process of (a) subjecting an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in one of the positions ortho and para to oxyalkylation with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the'class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula R10, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals; with the proviso that from about one-half to less than two moles of alkylene oxide be introduced for each phenolic nucleus; (b) converting said oxyalkylated resin into the corresponding alicyclic compound by hydrogenation in presence of a hydrogenating catalyst; (c) reacting said hydroaromatic compound with allyl glycidyl ether, with the proviso that at least 2 moles of allyl glycidyl ether be reacted for each alicyclic molecule and not in excess of three times the number of hydroxyl radicals present in said molecule; (d) polymerizing said allyl radical-containing derivative to yield an organic solvent-soluble product; (e) subjecting said aforementioned polymer to oxyethylation with (f) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; said oxyalkylated resin being characterized by the introduction into the resin molecule at hydroxyl groups, of a plurality of divalent radicals having the formula R10, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals; and with the final proviso that the hydrophile properties of said oxyalkylated resin in an equal Weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

3. The process of claim 2, wherein the aldehyde is formaldehyde.

4. The process of claim 2, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide.

5. The process of claim 2, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide, with the proviso that in the (a) section, the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to 1.

6. The process of claim 2, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide, with the proviso that in the (a) section, the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to 1; and with the further proviso that the molal ratio of allyl glycidal ether to the corresponding alicyclic hydroxyl be approximately 1 to 1.

7. The process of claim 2, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide, with the proviso that in the (a) section, the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to l; and with the further proviso that the molal ratio of allyl glycidyl ether to the corresponding alicyclic hydroxyl be approximately 1 to l; and with the final proviso that the radical R is a butyl radical.

8. The process of claim 2, wherein the aldehyde is formaldehyde and the alkylene oxide is ethyl- 29 ene oxide, with the proviso that in the (a) section, the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to 1, and with the further proviso that the molal ratio of allyl glycidyl ether to the corresponding alicyclic hydroxyl be approximately 1 to 1; and with the final proviso that the radical Ris an amyl radical.

9. The process of claim 2, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide, with the proviso that in the (a) section, the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to 1, and with the further proviso that the molal ratio of allyl glycidyl ether to the corresponding alicyclic hydroxyl be approximately 1 to 1; and with the final proviso that the radical R is an octyl radical.

10. The process of claim 1, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide, with the proviso that in the (a) section the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to 1, and with the further proviso that the molal ratio of allyl glycidyl ether to the corresponding alicyclic hydroxyl be approximately 1 to 1; and with the final proviso that the radical R is a nonyl radical.

11. The process of claim 1, wherein the aldehyde is formaldehyde and the alkylene oxide is ethylene oxide, with the proviso that in the (a) section, the molal ratio of ethylene oxide to initial phenolic hydroxyl be approximately 1 to 1, and with the further proviso that the molal ratio of allyl glycidyl ether to the corresponding alicyclic hydroxyl be approximately 1 to 1; and

with the final proviso that the radical R is a tetradecyl radical.

12. The product obtained by fined in claim 1.

13. The product fined in claim 2.

14; The product fined in claim 3.

15. The product fined in claim 4.

16. The product fined in claim 5.

1'7. The product fined in claim 6.

18. The product fined in claim 7.

19. The product fined in claim 8.

20. The product flnedinclaim 9.

21. The product fined in claim 10.

22. The product fined in claim 11.

the process deobtained by the process deobtained by the process deobtained by the process deobtained by the process deobtained by the process deobtained by the process dethe the

the

obtained by process deobtained by process deobtained by obtained by MELVIN DE GROOTE.

REFERENCES CITED The following references are of record in the file of this patent:

DIOGQSS (1% the process de- UNITED STATES PATENTS Number Name Date 2,528,932 Wiles Nov. 7, 1950 

4. THE PROCESS OF (A) SUBJECTING AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA: 